Advanced buckyball joints: synthesis, complex formation and computational simulations of centrohexaindane-extended tribenzotriquinacene receptors for C60 fullerene

Abstract

The synthesis of a structurally optimized tribenzotriquinacene receptor 9 is described, which is extended by centrohexaindane moieties to give rise to a half-round concave ball bearing, with optimum shape complementarity towards C₆₀ fullerene. Spectroscopic investigations reveal that this novel host forms a 1 : 1 host–guest complex with C₆₀ with a complex stability constant of K₁ = 14 550 ± 867 M⁻¹, which is considerably higher than those reported for structurally related tribenzotriquinacene hosts reported previously. Both the suppression for binding of a second receptor (i.e. formation of a 2 : 1 host–guest complex) as well as the increase of complex stability of the 1 : 1 complex can be rationalized in terms of multiple additive van der Waals and π–π interactions between C₆₀ and the aromatic groups of the receptor, as revealed by DFT + D and force-field calculations. Combining results from spectroscopic and theoretical investigations leads to predictions in light of future receptor designs, which – apart from shape complementarity – will have to consider an optimized electronic match (i.e. partial charge transfer) between the receptor and the fullerene host.